Open Journal of Inorganic Non-Metallic Materials, 2013, 3, 23-28

http://dx.doi.org/10.4236/ojinm.2013.33005 Published Online July 2013 (http://www.scirp.org/journal/ojinm)

Production of Iron from Mill Scale Industrial Waste via

Hydrogen
N. M. Gaballah1, A. F. Zikry1, M. G. Khalifa2, A. B. Farag1, N. A. El-Hussiny3, M. E. H. Shalabi3*
1
Faculty of Science, Helwan University, Cairo, Egypt
2
El-Tabbin Metallurgical Institute, Cairo, Egypt
3
Central Metallurgical Research and Development Institute, Cairo, Egypt
Email: *shalabimeh@hotmail.com.mail

Received November 16, 2012; revised December 15, 2012; accepted December 30, 2012

Copyright 2013 N. M. Gaballah et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

ABSTRACT
Mill scale is very attractive industrial waste due to its richness in iron (about = 72% Fe). In this paper, the characteriza-
tions of mill scale were studied by different methods of analyses. The produced mill scale briquettes were reduced with
hy- drogen at varying temperatures, and the reduction kinetics was determined. Two models were applied and the en-
ergy of activation was calculated.

Keywords: Mill Scale; Reduction by Hydrogen; Energy of Activation

1. Introduction stage of reduction and the activation energy about 80

In several iron and steel making processes, about 500
kg/ton of solid wastes of different nature are generated;
one of these wastes is the mill scale which represents
about 2% of steel produced [1]. Mill scale is a very at-
tractive industrial waste due to its richness in iron [about =
72 % Fe) [2].
In the whole world, 13.5 million tons of mill scales are
generated annually [3]. Mill scale is suitable for direct
recycling to the blast furnace via sintering plant [4]. Ap-
proximately, 90% of mill scale is directly recycled within
steelmaking industry and small amounts are used for
ferroalloys, in cement plants and in the petrochemicals
industry [5-8].
El-Hussiny et al. [9] studied the replacement of some
amount of Baharia high barite iron ore concentrate by mill
scale waste and they indicated that, replacement of some
iron ore by mill scale increased the amount of readymade
sinter, sinter strength and productivity of the sintering
machine and productivity of blast furnace yard.
The reduction of iron oxides via gaseous and solid re-
ductants has already been extensively studied [1].
Maurcio et al., studied the kinetics of scale reduction
by carbon monoxide in the temperature ranging in 800C -
1200C and the results indicated that un-reacted shrinking
core model with one interface under chemical reaction
control fits well with the experimental data at the initial
*
Corresponding author.
kJ/mol [1].
Benchiheub et al. [2] found that the best reduction of
mill scale was obtained at 1050C at 180 min in pure
carbon monoxide gas.
It was indicated that with increase in the temperature,
the percentage reduction increases with increase in time
and the activation energy of reduction depends upon the
type of binder [10].
Kawasaki et al. [11] found that varying total pressure of
the reduction system by hydrogen and carbon monoxide
had no effect on the rate of reduction. Commercial iron
powders are classified in three types, reduced iron powder,
atomized iron powder, and electrolytic iron powder, de-
pending on the production method and are used in various
applications, taking advantage of their respective proper-
ties.
Iron powders are used in many different industries for
many different applications. Followings are some exam-
ples of the iron powder uses: Brazing , Sintered Products,
Friction Products, Soft Magnetic Products, Chemicals,
Metallurgy, Filtration, Printing, Surface Coating, Welding,
Iron Fortification.
Iron powder cores are commonly used to produce high
Q inductors and transformers for selective circuits. Iron
powder cores used in RF applications are composed of
extremely small particles of highly pure carbonyl iron.
This study aims at investigating the reduction kinetic of

Copyright 2013 SciRes. OJINM

24 N. M. GABALLAH
Egyptian mill scale briquette via hydrogen to produce iron
powder.
2. Experimental Work
2.1. Material
The rolling mill scale used in this work was provided by
mill of Egyptian iron and steel Co. The sample was sub-
mitted to chemical and X-ray analysis was done by Bruc-
ker AXS_D8Advnce.
The chemical analyses of mill scale are illustrated in
Table 1.
Ray analysis is illustrated in Figure1. From which it is
clear that mill scale mainly consists of magnetite, wustite,
iron, quartz and hematite.
2.2. Preparation of the Briquetting and Its
Physical Properties
The mill scale was grinding in vibrating mill to powder
with size less than 75 micrometers. The mill scale powder
(10 g) are mixed with 2% molasses and then pressed under
different pressure (the pressure range from 75 MPa up to
275 MPa). The briquette subjected to drop number test
and crushing strength tests. The drop number indicates
how often green briquette can be dropped from a height 46
cm before they show perceptible cracks or crumble. Ten
green briquettes are individually dropped on to a steel
plate. The number of drops is determined for each bri-
quette. The arithmetical average values of the crumbing
behavior of the ten briquettes yield the drop number.
Table 1. The chemical analyses of mill scale.
Element Weight%
Fe (total) 69.33
Fe+2 49
Fe+3 12.5
FeO 7.83
S 0.33
P 0.22
Mn 0.51
Si 0.9
Figure 1. X-Ray analysis of mill scale sample.
Copyright 2013 SciRes.
ET AL.
The average crushing strength is done by compressed
10 briquettes between parallel steel plates up to their
breaking [12].
2.3. Reduction Process
The reduction of mill scale by hydrogen was done in a
thermo balance apparatus. (A schematic diagram of ther-
mo balance apparatus is shown in Figure 2 [13]. It con-
sisted of a vertical furnace, electronic balance for moni-
toring the weight change of reacting sample and tem-
perature controller. The sample was placed in a nickel
chrome crucible which was suspended under the electro-
nic balance by Ni-Cr wire. The furnace temperature was
raised to the required temperature (650C - 950C) and
maintained constant to 5C. Then samples were placed in
hot zone.
The nitrogen flow rate was 0.5 l/min in all the experi-
ments. At initial time air should be removed before each
experiment and also after the end of reduction. The weight
of the sample was continuously recorded at the end of the
run; the samples were withdrawn from the furnace and put
in the desiccators.
The percentage of reduction was calculated according
to the following equations:
W0 Wt 100
Percent of reduction =
Oxygen mass
where:
W0: the initial mass of mill scale sample after removal
of moisture.
Wt: mass of sample after each time, t.
Oxygen (mass): indicates the mass of oxygen percent in
mill scale in form FeO and Fe2O3.
Figure 2. A schematic diagram of thermo balance apparatus
(13).
OJINM
 N. M. GABALLAH
3. Results and Discussion
3.1. Effect of the Pressure Load with Constant
Amount of Binding Material on the Quality
of the Briquette
Figures 3 and 4 show the relation between the change of
pressure load at constant amount of molasses (2%) on the
drop number (drop damage resistance) and cold crushing
strength of the briquette It is clear that as the pressing
pressure load increased both the drop damage resistance
and crushing strength increased. This may be due to the
fact that increase pressure load increases the compaction
of briquette and subsequently the Vander Waals forces
increased [14,15], also the increase of briquetting pressure
leads to progressive crushing of the macro pores [16].
3.2. Effect of Flow Rate on the Degree of
Reduction
Figure 5 illustrated the effect of change hydrogen flow
rate on the degree of reduction of mill scale briquette at
900C (pressure load 216.85 MPa). From this figure it is
clear that the degree of reduction increased as the hydro-
gen flow rate increased. This may be attributed that the
increase of flow rate leads to an increase of number of
hydrogen mole in the bulk phase, which in turn leads to
the raise of hydrogen adsorption and subsequently the rate
of reaction increased [17] or the increase of flow rate
increased the gas diffusion across the boundary layer
Figure 3. Relationship between the change of pressure load
and drop no. of mill scale briquette.
Figure 4. Relationship between the change of pressure load
and cold crushing strength (C.S) of mill scale briquette.
Copyright 2013 SciRes.
ET AL. 25
Figure 5. Effect of change hydrogen flow rate on the degree
of reduction of mill scale briquette. (Pressure load 216.85
MPa, and temperature of reduction 900C).
subsequently the reduction ion increased [18]. Also may
be the higher flow rate prevailing in the reaction zone
which enhances the rate of hydrogen absorption and
subsequently the rate of chemical reaction steps increased
[19].
3.3. Effect of Temperature on the Reduction
Degree of Mill Scale Briquettes
Experiments were performed for briquette which pressed
at load 216. 85 MPa, in the temperature range of 650C to
950C in hydrogen atmosphere (2 L/min). Plots of the
reduction percentage as a function of time are shown in
Figure 6. From this figure, it is clear that the reduction
rates increased with increasing temperature. At high re-
duction temperatures (more than 900C and up to 950C),
with increasing temperature, the oxygen removal favor-
able increased.
The analyses of the curves relating the reduction per-
centage and time of reduction, shows that each curve has 3
different slopes indicating 3 different values of reduction
rates. The first value is high, while the second is some-
what slower and the third is slowest one. The increase of
reduction percentage with rise of temperature may be due
to the increase of number of reacting moles having excess
of energy which leads to the increase of reduction rate
[17,20]. Also the raise of temperature leads to an increase
of the rate of mass transfer of the diffusion and rate of
desorption [18-21].
3.4. Kinetics Reduction of Mill Scale
Briquette
Using two models:
1) Diffusion process controls equation Ginsling-Broun-
shtein [22,23].
1 2 3 R 1 R
23
=kt
OJINM
26 N. M. GABALLAH ET AL.

Figure 7. The relationship between time of reduction and 1

Figure 6. Effect of change temperature on the reduction (2/3) R (1 R) 2/3 at different temperatures.
degree of mill scale briquettes.

2) Diffusion process controls equation [24].

1 1 R
0.5
=kt
Where R is fractional reduction, t is time of reduction, k
is the rate constant.
Figure7, illustrates the relation between 1 (2/3) R (1
R) 2/3 against time of reduction for different reduction
temperatures. From which it is clear that the straight line
was observed.
The natural logarithms were used according to the Ar-
rhenius equation to calculate the activation energies of
reduction reaction. The results illustrate in Figure 8. From Figure 8. The relation between 1/T and ln K for first model
(Arrhenius plot for reduction reaction.
which it is clear that the activation energy = 72.25 kJ
/mole.
Figure 9 illustrate the relation between 1 (1 R)0.5
against time of reduction for different reduction tem-
perature. From which it is clear that the nearly straight
line was observed.
The natural logarithms were used according to the Ar-
rhenius equation to calculate the activation energies of
reduction reaction. The results illustrate in Figure 10
from which it is clear that the activation energy= 61.5
kJ/mole.

4. X-Ray Analysis of Some Reduced Samples

Figures 11 and 12 illustrate x-ray analyses of a reduced
mill scale at different temperatures (650C - 950C) in
hydrogen atmosphere. From which it is clear that the
reduction at high temperature more iron is produced and Figure 9. The relationship between time of reduction and 1
reached to about 100%. (1 R) 0.5 at different temperature.

5. Microscopic Analyses and pore.

Figures 13 and 14 show that the microscopic analyses of
the produced mill scale briquette in hydrogen atmos-
phere at temperatures 650C and 950C. From which it is
clear that the microscopic analyses of the reduced bri-
quette at 650C are wustite, iron and pore ,while the mi-
croscopic analyses of reduced briquette at 950C is iron
6. Conclusions
Mill scale is very attractive industrial waste due to its rich-
ness in iron (about = 72% Fe).
The pressing pressure loading in the briquetting process
of mill scale powder increased both the drop damage

Copyright 2013 SciRes. OJINM

 N. M. GABALLAH
Figure 10. The relation between 1/T and LnK for second
model (Arrhenius plot for reduction reaction.
Figure 11. X-ray analysis of sample produced at 650C.
Figure 12. X-ray analysis of sample produced at 950C.
(a) (b)
Figure13. Microscopic structure of the reduced mill scale
briquette at 650C. (a) X = 200; (b) X = 500.
resistance and crushing strength increased.
The degree of reduction of mill scale briquettes at cons-
tant temperature increased as the hydrogen flow rate in-
creased.
The reduction rate of mill scale briquettes under a cons-
Copyright 2013 SciRes.
ET AL. 27
(a) (b)
Figure 14. Microscopic structure of the reduced mill scale
briquette at 950C. (a) X = 200; (b) X = 500.
tant flow rate of hydrogen (as reducing agent) with in-
creasing temperature.
The kinetic reduction of mill scale briquettes shows that
the reduction process is controlled by diffusion process
and the energy of activation is ranged between (61.5 -
72.25 KJ/mol).
REFERENCES
[1] M. C. Bagatini, V. Zymla, E. Osrio and A. C. F. Vilela,
Characterization and Reduction Behavior of Mill Scale,
Isij International, Vol. 51, No. 7, 2011, pp. 1072-1079.
[2] O. Benchiheub, S. Mechachti, S. Serrai and M. G. Khalifa,
Elaboration of Iron Powder from Mill Scale, Journal of
Materials and Environmental Science, Vol. 1, No. 4,
2010, pp. 267-276.
[3] S. Cho and J. Lee, Metal Recovery from Stainless Steel
Mill Scale by Microwave Heating, Metals and Materials
International, Vol. 14, No. 2, 2008, pp. 193-196, 2005-
4149.
[4] A. M. Fleischanderl, Managing Steel Wastes and By-
Products: Crisis and Opportunity, Gorham/Intertechs
13th International Iron and Steel Development Forum,
Antwerp, 11-14 May 1998, pp. 45-50.
[5] Y.-K. Cho, Making Method for Ferrite Used Mill Scales,
Patent Kr 9103783, June 1991.
[6] D. Osing, Reuse of Metallurgical Fines, Patent Wo 96/
31630, 1996.
[7] A. Fleischanderl, J. Pesl and W. Gerbert, Aspect of Re-
cycling of Steelworks By-Products through the Bof,
Seaisi Quarterly, Vol. 28, No. 2, 1999, pp. 51-60.
[8] A. Poulalion, Process of Recycling Mill Scale of Alloy-
ed Steel in an Electric Furnace into a Ferro-Silicon Prod-
uct, Patent Ep 1122319, 2001.
[9] N. A. El-Hussiny, F. M. Mohamed and M. E. H. Shalabi,
Recycling of Mill Scale in Sintering Process, Since of
Sintering, Vol. 43, No. 1, 2011, pp. 21-31.
[10] S. Keshaarysingh and T. Krishnan, Reduction Kinetics
of Iron Ore Pellets and the Effect of Binders, Thesis of
Bachelor of Technology in Metallurgical and Materials
Engineering, Department of Metallurgical and Materials
Engineering National Institute of Technology Rourkela,
2008.
[11] E. Kawasaki, J. Sanscrainte and T. J. Walsh, Kinetics of
Reduction of Iron Oxide with Carbon Monoxide and Hy-
OJINM
28 N. M. GABALLAH
drogen, AIChE Journal, Vol. 8, No. 1, 1962, pp. 48-52.
doi:10.1002/aic.690080114
[12] K. Mayer, Pelletization Of Iron Ores, Springer-Verlag
Berlin Heidelberg, Berlin, Heidelberg 1980.
[13] N. A. El-Hussiny and M. E. H. Shalabi, A Self-Reduced
Intermediate Product from Iron and Steel Plant Waste
Material Using a Briquetting Process, Powder Technol-
ogy, Vol. 205, No. 1-3, 2011, pp. 217-223.
doi:10.1016/j.powtec.2010.09.017
[14] S. J. Mangena and V. M. Du Cann, Binderless Briquet-
ting of Some Selected South African Prim Coking, Blend
Coking and Weathered Bituminous Coals and the Effect
of Coal Properties on Binderless Briquetting, Interna-
tional Journal Of Coal Geology, Vol. 71, No. 2, 2007,
303-312.
[15] F. M. Mohamed, Y. M. Z. Ahmed and M. E. H. Shalabi,
Briquetting of Waste Manganese Ore Sinter Fine Using
Different Binding Materials, Environmental Issues and
Waste Management in Energy and Mineral Production
Swemp, 2004, pp. 567-573.
[16] O. G. Ingles, Microstructure in Binderless Briquetting,
Agglomeration, Interscience Publishers, New York, 1962,
pp. 29-53.
[17] M. E. Shalabi, The kinetics of reduction of Baharia iron
ores with hydrogen on static bed, M.Sc., El-Tabbin Met-
allurgical Institute for Higher Studies, 1973.
[18] S. A. Sayed, G. M. Khalifa, E. S. R. El-Faramawy and M.
E. H. Shalabi, Kinetic Reduction of Low Manganes Iron
Ore by Hydrogen, Egyptian Journal of Chemistry, Vol.
Copyright 2013 SciRes.
ET AL.
45, No. 1, 2002, pp.47-66.
[19] S. A. Sayed, M. G. Khalifa, E. S. R. El-Faramawy and M.
E. H. Shalabi, Reductions Kinetic of El-Baharia Iron Ore
in a Static Bed, Gospodarka Surowcami Mineranymi,
Vol. 17, Special Issue, 2001, pp. 241-245.
[20] M. E. H. Shalabi, O. A. Mohamed, N. A. Abdel-Khalek
and N. A. El-Hussiny, The Influence of Reduced Sponge
Iron Addition on the Quality of Produced Iron Ore Sin-
ter, Proceeding of the XXIMPC, Aachen, 21-26 Sep-
tember 1997, pp. 362-376.
[21] N. A. El-Hussiny, N. A. Abdel-Khalek, M. B. Morsi, O.
A. Mohamed, M. E. H. Shalabi and A. M. Baeka, Influ-
ence of Water Amount Added on the Sintering Process of
Egyptian Iron Ore, Gornictwo, Vol. 231, 1996, pp. 93-
115.
[22] Y. M. Wang and Z. F. Yuan, Reductive Kinetics of the
Reaction between a Natural Ilmenite and Carbon, Inter-
national Journal of Mineral Processing, Vol. 81, No. 3,
2006, pp. 133-140. doi:10.1016/j.minpro.2006.07.010
[23] L. L. C. Amci, S. U. Aydin and C. U. Arslan, Reduction
of Iron Oxides in Solid Wastes Generated by Steel-
works, Turkish Journal of Engineering and Environ-
mental Sciences, Vol. 26, No. 1, 2002, pp. 37-44.
[24] A. I. Sabry, A. N. Mahdy and M. F. Abadir, Thermal
Decomposition of MnCO3 in Air, Thermochimica Acta,
Vol. 98, No. 1, 1986, pp. 269-276.
doi:10.1016/0040-6031(86)87097-6
OJINM